Organotin miticidal and insecticidal compounds

ABSTRACT

A composition of matter is described herein which has insecticidal and miticidal activity and methods of use. The composition may be defined by the following generic formula ##STR1## wherein R 1  is lower alkyl having 1 to 4 carbon atoms, and R 2  can be selected from alkylketoximino, piperidyl, cycloalkylketoximino, alkylaldoximino, alkylcarbamylalkoxy, hexamethyleneimino, alkyloxazolidine, and ##STR2## wherein R 3  and R 4  can be the same or different and can be selected from hydrogen, alkyl having 1 to 15 carbon atoms, alkoxyalkyl, alkenyl, benzyl, cyanoalkyl, alkanol, phenyl, alkylphenyl, sulfonamidophenyl, thiazolinyl, alkoxycarbamyl, halobenzyl, furfuryl, provided that when R 3  is hydrogen, R 4  is other than hydrogen.

This is a division of application Ser. No. 466,928, filed on May 6,1974, now U.S. Pat. No. 3,947,461, Mar. 30, 1976, which in turn is adivision of application Ser. No. 304,871, filed Oct. 19, 1972, now U.S.Pat. No. 3,832,370, Aug. 27, 1974.

BACKGROUND OF THE INVENTION

Among the many insecticidal and miticidal compounds available, theorganotin compounds have reached a relatively high degree of commericalsuccess. Specifically, the organotins described in U.S. Pats. No.3,264,177, 3,591,614 and 3,591,615 are widely used. These compounds,however, suffer from considerable unstability due to the presence of anester linkage to the tin atom. Thus, these compounds are quitesusceptible to hydrolysis on use. Additionally, the organotin compoundsdescribed in U.S. Pats. No. 3,321,361 and 3,321,365 are useful asinsecticides. However, these compounds are quite toxic to vegetation andthus have extremely limited use.

BRIEF DESCRIPTION OF THE INVENTION

It has been discovered that certain organotin compounds have relativelylow phytotoxicity properties and are relatively stable. These organotincompounds may be defined by the following generic formula ##STR3##wherein R₁ is lower alkyl having 1 to 4 carbon atoms, and R₂ can beselected from alkylketoximino, piperidyl, cycloalkylketoximino,alkylaldoximino, alkylcarbamylalkoxy, hexamethyleneimino,alkyloxazolidine, and ##STR4## wherein R₃ and R₄ can be the same ordifferent and can be selected from hydrogen, alkyl having 1 to 15 carbonatoms, alkoxyalkyl, alkenyl, benzyl, cyanoalkyl, alkanol, phenyl,alkylphenyl, sulfonamidophenyl, thiazolinyl, alkoxycarbamyl, halobenzyl,furfuryl, provided that when R₃ is hydrogen, R₄ is other than hydrogen.

DETAILED DESCRIPTION OF THE INVENTION

In the practice of the present invention, the compounds of the presentinvention are manufactured by reacting an alkylthiophosphine sulfidewith an appropriate amine in a neutral solvent to form an intermediatecompound. The intermediate compound is then reacted with an alkyl tinhalide to form the end product. The halide moiety in the alkyl tinhalide can be selected from the group consisting of chlorine, bromineand iodine. After the compounds of the present invention are formed,they can be applied to the habitat in an effective amount to controlrespective mites and insects.

The following examples illustrate the merits of the present invention:

EXAMPLE 1 ##STR5##

A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. of tetrahydrofuran, 2.8 grams (0.015mole) of dodecylamine and 7.0 ml. of triethylamine. This mixture wasallowed to stand for 1 hour wherein 6.1 grams (0.015 mole) oftricyclohexyl tin chloride was added and the mixture was allowed tostand for 24 hours. Then, the mixture was heated to boiling for a fewminutes, then diluted with 100 ml. of chloroform, washed with 100 ml. ofwater and 50 ml. of sodium bicarbonate solution, dried over magnesiumsulfate and evaporated in vacuo to yield 6.5 grams of product.

EXAMPLE 2 ##STR6##

A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. tetrahydrofuran, and 3.0 grams (0.04mole) of methoxyethylamine. The mixture was allowed to stand for 1 hour,wherein 6.1 grams (0.015 mole) of tricyclohexyl tin chloride was added.The mixture was allowed to stand for 24 hours. Then, the mixture washeated to boiling for a few minutes, diluted with 100 ml. of chloroform,washed with 100 ml. of water and a 50 ml. solution of sodiumbicarbonate, dried over magnesium sulfate and evaporated in vacuo toyield 6.5 grams of product, m.p. 56°-59° C.

EXAMPLE 3 ##STR7##

A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. of ethyl ether and 4.1 ml. (0.04mole) of diethylamine. This mixture was allowed to stand for 1 hour.Then, 6.1 grams (0.015 mole) of tricyclohexyl tin chloride and 50 ml.tetrahydrofuran was added and the mixture was allowed to stand for 24hours. Then, the mixture was boiled for a few minutes, diluted with 50ml. of ethyl ether and then washed with 100 ml. of water, 50 ml. of asaturated solution of sodium bicarbonate, dried over magnesium sulfateand evaporated in vacuo to yield 7.0 grams of product.

EXAMPLE 4 ##STR8##

A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. tetrahydrofuran, 1.70 grams (0.015mole) of cyclohexanoneoxime and 7.0 ml. of triethylamine. This mixturereacted exothermically with the addition of triethylamine. After 1 hour,6.0 grams (0.015 mole) of tricyclohexyl tin chloride was added andallowed to stand for 2 days. The mixture was diluted with 100 ml. ofchloroform. The mixture was then washed with 100 ml. of water, 50 ml. ofsaturated sodium bicarbonate solution, dried over magnesium sulfate andevaporated in vacuo to yeild an oil that was triturated with methanol toyeild 7.2 g. of crystals, m.p. 76°-79° C.

EXAMPLE 5 ##STR9##

The procedure of Example 4 was repeated in its entirety except 1.8 grams(0.019 mole) of aniline was substituted for the 1.70 grams ofcyclohexanoneoxime. The yield was 6.0 grams of product, m.p. 88°-90° C.

EXAMPLE 6 ##STR10##

The procedure of Example 4 was repeated in its entirety except 1.37grams (0.015 mole) of methylhydrazinocarboxylate was substituted for the1.70 grams of cyclohexanoneoxime and only a 24 hour reaction period wasused instead of 2 days. The yield was 5.0 grams of product, m.p. 83°-86°C.

EXAMPLE 7 ##STR11##

A mixture was formed containing 2.2 grams (0.009 mole) ofethylthiophosphine sulfide, 50 ml. tetrahydrofuran, 2.0 ml. (0.02 mole)n-butylamine, and 7.0 ml. of triethylamine. After standing at roomtemperature for 1 hour, 5.0 grams (0.0124 mole) of tricyclohexyl tinchloride was added in one portion and the mixture was allowed to standuntil the next morning. The mixture was diluted with 100 ml. ofchloroform and then washed with 100 ml. of water, 50 ml. of 1N HCl, 50ml. of saturated sodium bicarbonate solution and then dried overmagnesium sulfate and evaporated in vacuo to give an oil that wascrystallized from 50 ml. of methyl alcohol to yield 6.0 grams ofproduct, m.p. 58°-60° C.

EXAMPLE 8 ##STR12##

The procedure of Example 7 was repeated in its entirety except 1.1 gramsof methylamine gas was substituted for the n-butylamine. The productyield was 3.8 grams, m.p. 81°-83° C.

Other compounds were made in a similar manner using appropriate startingmaterials. The compounds are listed in Table I. ##STR13##

INSECTICIDAL EVALUATION TESTS

The following insect species are subjected to evaluation tests forinsecticidal activity.

(1) Housefly (HF) -- Musca domestica (Linn.)

(2) Lygus Bug (LB) -- Lygus hesperus (Knight)

(3) Bean Aphid (BA) -- Aphis fabae (Scop.)

(4) Two-spotted Mite (2-SM) -- Tetranychus urticae (Koch)

(5) Salt-Marsh Caterpillar (SMC) -- Estigmene acrea (Drury)

(6) Beet armyworm (BAW) -- Spodoptera exigua (Hubner)

(7) Tobacco budworm (TBW) -- Heliothis virescens (Fabricius)

Aliquots of the toxicants, dissolved in an appropriate solvent, arediluted in water containing 0.018% of a wetting agent, Sponto 221® (apolyoxyether of alkylated phenols blended with organic sulfonates). Testconcentrations range from 0.1% downward to that at which 50% mortalityis obtained. In the tests, for these species, ten 1-month old nymphs ofthe Lygus Bug are placed in a circular cardboard cage sealed on one endwith cellophane and covered by a cloth netting on the other. Testconcentrations for the Lygus Bug ranged from 0.05% downward to that atwhich 50% mortality was obtained. Each of the aqueous suspensions of thecandidate compounds are sprayed onto the insects through the clothnetting by means of a hand spray gun. Per cent mortality in each case isrecorded after 72 hours, and the LD₅₀ value expressed as per cent oftoxicant in the aqueous spray is recorded. The results are in Table IIunder Column LB.

The following procedure is used to test houseflies: A stock solutioncontaining 0.1 per cent by weight of the toxicant in an appropriatesolvent is prepared. Aliquots of this solution are combined with 1milliliter of an acetone-peanut oil solution in a 60 mm O.D. aluminumpan and allowed to dry. The aliquots are selected to achieve desiredtoxicant concentration ranging from 100 μg per aluminum pan to that atwhich 50% mortality was attained. The aluminum pans are placed in acircular cardboard cage, closed on the bottom with cellophane andcovered on top with cloth netting. Twenty-five female houseflies areintroduced into the cage and the per cent mortality is recorded after 48hours. The LD₅₀ values are expressed in terms of μg per 25 female flies.LD₅₀ values obtained in the above-mentioned housefly test are found inTable II under Column HF.

The compound is dissolved in the appropriate solvent and diluted to aconcentration of 0.1 per cent with water containing 0.018% Sponto 221®.A portion of the leaf from a bitter dock (Rumex obtusifolius) plant isimmersed in the test solution for 10 seconds and allowed to dry. Whendry, the leaf is placed in a Petri dish containing a 9 cm disc ofmoistened filter paper. Five 3rd-instar saltmarsh caterpillar larvae areplaced on the treated leaf. Mortality is recorded after 72 hours. Testconcentrations range from 0.1 per cent to that at which 50% mortality isobtained. This latter concentration is recorded as the LD₅₀ value forthe test compound.

The test method for the cotton bollworm, beet armyworm and tobaccobudworm is identical to the above except that Romaine lettuce (Lactucasativa) is used as the test plant rather than bitter dock.

The compounds are also active against two-spotted mite (2-SM)Tetranychus urticae (Koch). Pinto bean plants (Phaseolus sp.) areutilized as the host plant and infested with 50 to 75 mites of variousages. Twenty-four hours after infestation, they are sprayed to the pointof run off with aqueous suspension of the toxicant. Test concentrationsrange from 0.05% to that at which 50% mortality is obtained. The valuesobtained in this test are found in Table II under the Columns 2SM-PE and2SM-Eggs.

The compounds are also active against bean aphid (Aphis fabae (Scop.))as a contact toxicant. The same test procedure as given for thetwo-spotted mite above is used for the bean aphid except nasturtium(Tropaeolum Sp.) plants approximately 2 to 3 inches tall are used as thehost plant. The LD₅₀ values obtained for the compounds of this inventionare found in Table II under Column BA.

                                      TABLE II                                    __________________________________________________________________________    Ex.               2-SM                                                        No.                                                                              HF  LB   BA    PE  Eggs                                                                              SMC  BAW  TBW                                       __________________________________________________________________________    1  80  >.05 0.01  .0003                                                                             .0008                                                                             .03  .03  .1                                        2  50  >.05 >.05  .0003                                                                             .0008                                                                             .01  .01  .1                                        3  75  >.05 .01   .0001                                                                             .003                                                                              .03  .01  >.1                                       4  65  >.05 .003  .0003                                                                             .003                                                                              >.1  .03  >.1                                       5  65  >.05 .008  .003                                                                              .003                                                                              >.1  .01  >.1                                       6  65  >.05 .03   .0003                                                                             .003                                                                              .1   .08  >.1                                       7  65  >.05 .03   .0003                                                                             .0008                                                                             .03  .008 >.1                                       8  65  >.05 .03   .0003                                                                             .0008                                                                             .05  .008 >.1                                       9  40  .05  .05   .0003                                                                             .003                                                                              --   --   >.1                                       10 50  .05  .03   .0001                                                                             .003                                                                              --   --   >.1                                       11 80  .02  .03   .0003                                                                             .003                                                                              --   --   >.1                                       12 55  .05  .01   .0005                                                                             .003                                                                              .01  .03  .1                                        13 60  .05  .01   .0003                                                                             .003                                                                              .1   .03  >.1                                       14 80  .05  .01   .0003                                                                             .0008                                                                             .1   .01  >.1                                       15 80  >.05 .05   .0003                                                                             .003                                                                              .05  .01  >.1                                       16 >100                                                                              >.05 >.05  .003                                                                              .03 >.1  --   --                                        17 80  .05  .03   .0003                                                                             .0008                                                                             >.1  .01  >.1                                       18 90  .05  .03   .001                                                                              .008                                                                              >.1  .01  >.1                                       19 90  .05  .008  .0005                                                                             .008                                                                              .1   .01  .1                                        20 >100                                                                              >.05 .03   .001                                                                              .008                                                                              >.1  .01  >.1                                       21 65  >.05 .01   .0003                                                                             .003                                                                              .1   .1   >.1                                       22 65  >.05 .05   .0003                                                                             .003                                                                              .1   .1   >.1                                       23 65  >.05 .03   .0003                                                                             .003                                                                              >.1  .05  >.1                                       24 65  >.05 .01   .0003                                                                             .003                                                                              .1   .05  >.1                                       25 65  >.05 .005  .0003                                                                             .003                                                                              >.1  .05  >.1                                       26 65  .05  .008  .0001                                                                             .0008                                                                             .05  .005 .08                                       27 65  >.05 .005  .0003                                                                             .003                                                                              .05  .01  >.1                                       28 65  >.05 .03   .0003                                                                             .0008                                                                             >.05 .01  >.1                                       29 65  >.05 .008  .0005                                                                             .0008                                                                             .03  .005 >.1                                       30 65  .05  .008  .0003                                                                             .003                                                                              .05  .005 >.1                                       31 80  >.05 .03   .0003                                                                             .0008                                                                             .05  .005 >.1                                       32 65  >.05 .03   .0003                                                                             .0008                                                                             > .1 .005 >.1                                       33 65  >.05 .03   .0003                                                                             .0008                                                                             .1   .005 .08                                       34 65  >.05 .03   .0003                                                                             .0008                                                                             >.1  .01  .05                                       35 65  >.05 .03   .0001                                                                             .003                                                                              .1   .005 .1                                        __________________________________________________________________________

The compounds of this invention are generally embodied into a formsuitable for convenient application. For example, the compounds can beembodied into pesticidal compositions which are provided in the form ofemulsions, suspensions, solutions, dusts and aerosol sprays. In general,such compositions will contain, in addition to the active compound, theadjuvants which are found normally in pesticide perparations. In thesecompositions, the active compounds of this invention can be employed asthe sole pesticide component or they can be used in admixture with othercompounds having similar utility. The pesticide compositions of thisinvention can contain, as adjuvants, organic solvents, such as sesameoil, xylene range solvents, heavy petroleum, etc.; water; emulsifyingagents; surface active agents; talc; pyrophyllite; diatomite; gypsum;clays; propellants, such as dichlorodifluoromethane, etc. If desired,however, the active compounds can be applied directly to feedstuffs,seeds, etc. upon which the pests feed. When applied in such a manner, itwill be advantageous to use a compound which is not volatile. Inconnection with the activity of the presently disclosed pesticidalcompounds, it should be fully understood that it is not necessary thatthey be active as such. The purposes of this invention will be fullyserved if the compound is rendered active by external influences, suchas light or by some physiological action which occurs when the compoundis ingested into the body of the pest.

The precise manner in which the pesticidal compositions of thisinvention are used in any particular instance will be readily apparentto a person skilled in the art. Generally, the active pesticide compoundwill be embodied in the form of a liquid composition; for example, anemulsion, suspension, or aerosol spray. While the concentration of theactive pesticide in the present compositions can vary within rather widelimits, ordinarily the pesticide compound will comprise not more thanabout 50.0% by weight of the composition. Preferably, however, thepesticide compositions of this invention will be in the form of spraytank solutions or suspensions containing about 0.1 to 1.0% by weight ofthe active pesticide compound.

What is claimed is:
 1. A compound having the formula ##STR14## whereinR₁ is lower alkyl having 1 to 4 carbon atoms, and R₂ is selected fromthe group consisting of piperidyl and hexamethyleneimino, attachedthrough the nitrogen.
 2. A compound of claim 1 wherein R₁ is C₂ H₅ andR₂ is ##STR15##
 3. A compound of claim 1 wherein R₁ is C₂ H₅ and R₂ is##STR16## .